Method for preparing sulfated metal oxide catalyst for chlorination, and chlorination method using sulfated metal oxide catalyst

Abstract

The present invention relates to a method for preparing a sulfated metal oxide catalyst for chlorination, and a method for producing a reaction product containing methyl chloride (CH 3 Cl) by using the sulfated metal oxide catalyst. A sulfated zirconia catalyst and a sulfated tin oxide catalyst are disclosed as the sulfated metal oxide catalyst for chlorination.

The invention claimed is: 
     
       1. A method for producing a reaction product containing methyl chloride (CH 3 Cl),
 wherein the method comprises: 
 a step a) of forming a mixed solution by mixing an amine reactant and a zirconium precursor containing an oxygen element and dissolving the mixture in a solvent; 
 a step b) of forming a gel-type product by heating and stirring the mixed solution formed in the step a); 
 a step c) of forming zirconia (ZrO 2 ) by calcining the gel-type product formed in the step b); 
 a step d) of preparing sulfated zirconia (SO 4   2- /ZrO 2 ) by impregnating the zirconia formed in the step c) with a solution containing a sulfated agent and evaporating the solvent by performing heating; 
 a step e) of calcining the sulfated zirconia prepared in the step d) at 500 to 800° C. under an air atmosphere and thereby preparing a sulfated zirconia catalyst for chlorination; and 
 a step f) of performing a chlorination reaction on gaseous reactants consisting of methane (CH 4 ) and chlorine (Cl 2 ) gas under a presence of the sulfated zirconia catalyst for chlorination prepared in the step e). 
 
     
     
       2. The method of  claim 1 , wherein the chlorination reaction is performed:
 (i) at a temperature of 200 to 550° C.; 
 (ii) at a molar ratio of methane to chlorine (Cl 2 ) gas of 1/1 to 10/1; and 
 (iii) at a gas hourly space velocity (GHSV) of each of the reactants of 100 to 3000 cc/g/h. 
 
     
     
       3. A method for producing a reaction product containing methyl chloride (CH 3 Cl) by performing a chlorination reaction on gaseous reactants consisting of methane (CH 4 ) and chlorine (Cl 2 ) gas under a presence of a sulfated tin oxide catalyst for chlorination prepared by a preparation method,
 wherein the preparation method comprises: 
 a step a) of dissolving a tin precursor in a solvent and inducing hydrolysis of the tin precursor by adding aqueous ammonia until a pH of a solution reaches 7.5 or more; 
 a step b) of obtaining a solid product by filtering a precipitate obtained by the hydrolysis in the step a); 
 a step c) of producing tin hydroxide (Sn(OH) 4 ) by drying the solid product obtained in the step b); 
 a step d) of obtaining a solid product by impregnating the tin hydroxide (Sn(OH) 4 ) produced in the step c) with a solution containing a sulfated agent, stirring the solution and performing filtering; 
 a step e) of drying the solid product obtained in the step d); and 
 a step f) of producing sulfated tin oxide by calcining the solid product dried in the step e). 
 
     
     
       4. The method of  claim 3 , wherein the chlorination reaction is performed:
 (i) at a temperature of 200 to 550° C.; 
 (ii) at a molar ratio of methane to chlorine (Cl 2 ) gas of 1/1 to 10/1; and 
 (iii) at a gas hourly space velocity (GHSV) of each of the gaseous reactants of 100 to 3000 cc/g/h. 
 
     
     
       5. A method for producing a reaction product containing methyl chloride (CH 3 Cl) by performing a chlorination reaction on a gaseous reactants consisting of methane (CH 4 ) and chlorine (Cl 2 ) gas under a presence of a sulfated zirconia catalyst for chlorination,
 wherein a total acid density of the catalyst measured by ammonia temperature-programmed desorption (NH 3 -TPD) is 8 mmolNH 3 /g or more, and a proportion of an acid density of a very strong acid site (an acid site at which an acid site desorption temperature is higher than 400° C.) is 80% or more of the total acid density. 
 
     
     
       6. A method for producing a reaction product containing methyl chloride (CH 3 Cl) by performing a chlorination reaction on gaseous reactants consisting of methane (CH 4 ) and chlorine (Cl 2 ) gas under a presence of a sulfated tin oxide catalyst for chlorination. 
     
     
       7. The method of  claim 5 , wherein a content of sulfate ions (SO 4   2- ) in the catalyst is 10.0 wt % or more. 
     
     
       8. The method of  claim 6 , wherein a content of sulfate ions (SO 4   2- ) in the catalyst is 5.0 wt % or more. 
     
     
       9. The method of  claim 6 , wherein a total acid density of the catalyst measured by ammonia temperature-programmed desorption (NH 3 -TPD) is 3.0 mmolNH 3 /g or more, and
 a proportion of an acid density of a very strong acid site (an acid site at which an acid site desorption temperature is higher than 400° C.) is 50% or more of the total acid density. 
 
     
     
       10. The method of  claim 6 , wherein a BET specific surface area of the catalyst is 80 to 200 m 2 /g.